EP1153927B1 - Process for preparing yellow bis(3-[triethoxysilyl]propyl)tetrasulfan - Google Patents

Process for preparing yellow bis(3-[triethoxysilyl]propyl)tetrasulfan Download PDF

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EP1153927B1
EP1153927B1 EP01111617A EP01111617A EP1153927B1 EP 1153927 B1 EP1153927 B1 EP 1153927B1 EP 01111617 A EP01111617 A EP 01111617A EP 01111617 A EP01111617 A EP 01111617A EP 1153927 B1 EP1153927 B1 EP 1153927B1
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triethoxysilyl
propyl
chloropropyltriethoxysilane
iodine
neutral
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EP1153927A3 (en
EP1153927A2 (en
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Roland Dr. Krafczyk
Ulrich Dr. Deschler
Rudolf Michel
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Evonik Operations GmbH
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Degussa GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888

Definitions

  • the invention relates to the preparation of yellow bis (3- [triethoxysilyl] propyl) tetrasulfan.
  • the object of the invention is an alternative method to provide a yellow bis (3- [triethoxysilyl] propyl) tetrasulfane receives.
  • the invention relates to a process for the preparation of yellow bis (3- [triethoxysilyl] propyl) tetrasulfan having an iodine color number of ⁇ 10 mg iodine / 100 ml, preferably 5-7 mg iodine / 100 ml, which is characterized in that chloropropyltrichlorosilane is added to neutral chloropropyltriethoxysilane and then reacted with sodium polysulfide or Na 2 S and sulfur in ethanol.
  • This method has the advantage that the Ethanolysis reaction not very specific to a particular Point must be aborted shortly before full turnover, but until complete conversion to neutral Chloropropyltriethoxysilane can be carried out.
  • Chloropropyltrichlorosilane to a solution of neutral Chloropropyltriethoxysilane and ethanol or Chloropropyltrichlorosilane to neutral Chloropropyltriethoxysilane and then add ethanol.
  • Chloropropyltrichlorosilane can be used in amounts of from 0.1 to 20% by weight, preferably 0.5 to 5 wt .-%, particularly preferably 0.8 to 1.2 % By weight, based on chloropropyltriethoxysilane, be added.
  • the reaction mixture may be heated before the addition of sodium polysulfide or Na 2 S and sulfur, preferably at temperatures of 20-90 ° C.
  • Bis (3- [triethoxysilyl] propyl) tetrasulfane prepared according to The process according to the invention has an iodine color number of ⁇ 10 mg iodine / 100 ml.
  • chloropropyltrichlorosilane are added dropwise to a solution of 240.8 g of chloropropyltriethoxysilane (neutral) in 200 ml of ethanol. It is then boiled for 1 h at 82 ° C with stirring at reflux. After cooling to 60 ° C., 87.1 g of sodium polysulfide are added and the reaction mixture is refluxed for 1.5 hours at 82 ° C. with stirring. After cooling to room temperature, the precipitated sodium chloride is filtered off and the ethanol is removed on a rotary evaporator.
  • chloropropyltrichlorosilane are added dropwise to 240.8 g of chloropropyltriethoxysilane (neutral). The mixture is then stirred for 1 h at 80 ° C. After addition of 200 ml of ethanol, the temperature drops to 62 ° C, 87.1 g of sodium polysulfide are added and the reaction mixture is refluxed for 1.5 hours at 82 ° C with stirring. After cooling to room temperature, the precipitated sodium chloride is filtered off and the ethanol is removed on a rotary evaporator.
  • Chlorporpyltrichlorsilan are added dropwise to a solution of 481.6 g of chloropropyltriethoxysilane (neutral) in 450 ml of ethanol. It is then boiled for 1 h at 80 ° C with stirring at reflux. After cooling to 58 ° C., 89.8 g of sodium sulfide and 105.8 g of sulfur are added and the reaction mixture is refluxed for 1.5 hours at 82 ° C. with stirring. After cooling to room temperature, the precipitated sodium chloride is filtered off and the ethanol is removed on a rotary evaporator.
  • Example 7 (Comparative Example 3):
  • Chloropropyltriethoxysilane neutral
  • Chloropropyltrichlorosilane 1 h stirred long at 80 ° C.
  • Chloropropyltriethoxysilane neutral
  • GC-MS Chloropropyltriethoxysilane
  • GC HP 5890 II; MS: Finnigan MAT 95; Column: 30 m x 0.25 mm DB-5MS; df: 0.25 ⁇ m U026; Helium: 80 kPa; Temp .: 50 (5) -5-100-15-300 (10); Split: 100 ml / min; Inj.vol .: 0.1 ⁇ l dissolved in n-hexane.
  • the iodine color number is determined according to DIN 6162.

Description

Die Erfindung betrifft die Herstellung von gelbem Bis(3-[triethoxysilyl]propyl)tetrasulfan.The invention relates to the preparation of yellow bis (3- [triethoxysilyl] propyl) tetrasulfan.

Aus DE 21 41 159 ist die Herstellung von Bis(3-[triethoxysilyl]propyl)tetrasulfan (Si 69) durch Umsetzung von Chlorpropyltriethoxysilan mit Natriumpolysulfid (NPS) bekannt. Das verwendete Chlorpropyltriethoxysilan kann durch Ethanolyse von Chlorpropyltrichlorsilan hergestellt werden. Dabei wird nach bekannten Verfahren, wie in DE 20 61 189 und DE 32 36 628 beschrieben, ein vollständig umgesetztes Produkt mit einem nur sehr geringen Anteil an Chlorpropylmonochlordiethoxysilan erhalten. Dieses vollständig umgesetzte Chlorpropyltriethoxysilan wird im folgenden "neutral" genannt.From DE 21 41 159 is the preparation of bis (3- [triethoxysilyl] propyl) tetrasulfan (Si 69) by reaction of Chloropropyltriethoxysilane with Sodium Polysulfide (NPS) known. The chloropropyl triethoxysilane used can produced by ethanolysis of chloropropyltrichlorosilane become. In this case, by known methods, as in DE 20 61 189 and DE 32 36 628, a complete reacted product with a very small proportion of Chloropropyl monochlorodiethoxysilane obtained. This completely reacted chloropropyltriethoxysilane is used in following called "neutral".

Wird das neutrale Chlorpropyltriethoxysilan mit Natriumpolysulfid oder Na2S und Schwefel zur Herstellung von Bis(3-[triethoxysilyl]propyl)tetrasulfan nach dem Verfahren beschrieben in DE 21 41 159 umgesetzt, so wird ein dunkelgelb bis rot gefärbtes Produkt (Iodfarbzahl ≥ 20 mg Iod/100 ml) erhalten. Am Markt eingeführt ist jedoch ein hellgelbes Produkt, das aus neutralem Chlorpropyltriethoxysilan nicht zugänglich ist. Um hellgelbes Bis(3-[triethoxysilyl]propyl)tetrasulfan (Iodfarbzahl ≤ 10 mg Iod/100 ml) zu erhalten, muß im Chlorpropyltriethoxysilan ein sogenannter Restsäuregehalt in Form von Chlorpropylmonochlordiethoxysilan vorhanden sein. Dies kann dadurch erreicht werden, daß die Ethanolysereaktion nicht vollständig zu Ende geführt wird. Diese Maßnahme bedingt in der betrieblichen Praxis jedoch einen nicht unerheblichen Mehraufwand, insbesondere deshalb, weil der Restsäuregehalt in einem sehr engen Bereich gehalten werden muß, die Reaktion also sehr gezielt an einem bestimmten Punkt kurz vor vollständigem Umsatz abgebrochen werden muß.If the neutral chloropropyltriethoxysilane is reacted with sodium polysulfide or Na 2 S and sulfur to prepare bis (3- [triethoxysilyl] propyl) tetrasulfane according to the process described in DE 21 41 159, a dark yellow to red-colored product (iodine color number ≥ 20 mg iodine / 100 ml). However, a light yellow product that is not available from neutral chloropropyltriethoxysilane has entered the market. In order to obtain pale yellow bis (3- [triethoxysilyl] propyl) tetrasulfan (iodine color number ≦ 10 mg iodine / 100 ml), a so-called residual acid content in the form of chloropropyl monochlorodiethoxysilane must be present in the chloropropyltriethoxysilane. This can be achieved by not completely completing the ethanolysis reaction. However, this measure requires in practice a considerable additional effort, in particular because the residual acid content must be kept within a very narrow range, so the reaction must be terminated very targeted at a certain point shortly before complete sales.

Auch eine Ansäuerung des neutralen Chlorpropyltriethoxysilans mit alkoholischer Salzsäure vor der Reaktion mit den genannten Schwefelungsagentien führt nicht zu hellgelb gefärbtem Bis(3-[triethoxysilyl]propyl)tetrasulfan, sondern ebenfalls zu dunkelgelb bis rot gefärbtem.Also an acidification of the neutral Chloropropyltriethoxysilane with alcoholic hydrochloric acid before the reaction with the said sulfurizing agents leads not to light yellow colored bis (3- [triethoxysilyl] propyl) tetrasulfan, but also too dark yellow to red colored.

Der Nachteil dieser bekannten Verfahren besteht darin, daß ein Produkt mit dunkelgelber bis roter Farbe erhalten wird.The disadvantage of these known methods is that a product with dark yellow to red color is obtained.

Aufgabe der Erfindung ist es, ein alternatives Verfahren bereitzustellen, mit dessen Hilfe man ein gelbes Bis(3-[triethoxysilyl]propyl)tetrasulfan erhält.The object of the invention is an alternative method to provide a yellow bis (3- [triethoxysilyl] propyl) tetrasulfane receives.

Gegenstand der Erfindung ist ein Verfahren zur Herstellung von gelbem Bis(3-[triethoxysilyl]propyl)tetrasulfan mit einer Iodfarbzahl von ≤ 10 mg Iod/100 ml, vorzugsweise 5-7 mg Iod/100 ml, welches dadurch gekennzeichnet ist, daß man zu neutralem Chlorpropyltriethoxysilan Chlorpropyltrichlorsilan gibt und anschließend mit Natriumpolysulfid oder Na2S und Schwefel in Ethanol umsetzt.The invention relates to a process for the preparation of yellow bis (3- [triethoxysilyl] propyl) tetrasulfan having an iodine color number of ≤ 10 mg iodine / 100 ml, preferably 5-7 mg iodine / 100 ml, which is characterized in that chloropropyltrichlorosilane is added to neutral chloropropyltriethoxysilane and then reacted with sodium polysulfide or Na 2 S and sulfur in ethanol.

Die Zugabe von geringen Mengen an Chlorpropyltrichlorsilan zu neutralem Chlorpropyltriethoxysilan kann zur Bildung von geringen Mengen an Chlorpropylmonochlordiethoxysilan und Chlorpropyldichlormonoethoxysilan führen (1). (EtO)3Si-R + Cl3Si-R → (EtO)2ClSi-R + (EtO)Cl2 Si-R    mit R = (CH2)3ClThe addition of small amounts of chloropropyltrichlorosilane to neutral chloropropyltriethoxysilane can lead to the formation of small amounts of chloropropylmonochlorodiethoxysilane and chloropropyldichloromonoethoxysilane (1). (EtO) 3 Si-R + Cl 3 Si-R → (EtO) 2 ClSi-R + (EtO) Cl 2 Si-R with R = (CH 2 ) 3 Cl

Die Bildung von Chlorpropylmonochlordiethoxysilan und Chlorpropyldichlormonoethoxysilan, selbst bei Abwesenheit eines Lösungsmittels wie zum Beispiel Ethanol, kann durch GC-MS Untersuchungen bestätigt werden. The formation of chloropropylmonochlorodiethoxysilane and Chloropropyldichloromonoethoxysilane, even in the absence a solvent, such as ethanol, can by GC-MS examinations are confirmed.

Dieses Verfahren hat den Vorteil, daß die Ethanolysereaktion nicht sehr gezielt an einem bestimmten Punkt kurz vor vollständigem Umsatz abgebrochen werden muß, sondern bis zur vollständigen Umsetzung zu neutralem Chlorpropyltriethoxysilan durchgeführt werden kann. Die für die Herstellung von hellgelbem Bis(3-[triethoxysilyl]propyl)tetrasulfan erforderliche kleine Menge an Chlorpropylmonochlordiethoxysilan kann einfach durch Zugabe von Chlorpropyltrichlorsilan zu neutralem Chlorpropyltriethoxysilan erreicht werden.This method has the advantage that the Ethanolysis reaction not very specific to a particular Point must be aborted shortly before full turnover, but until complete conversion to neutral Chloropropyltriethoxysilane can be carried out. The for the preparation of pale yellow bis (3- [triethoxysilyl] propyl) tetrasulfan required small Amount of chloropropylmonochlorodiethoxysilane can be simple by adding chloropropyltrichlorosilane to neutral Chloropropyltriethoxysilane can be achieved.

Die Dosierreihenfolge ist unerheblich. Man kann Chlorpropyltrichlorsilan zu einer Lösung aus neutralem Chlorpropyltriethoxysilan und Ethanol geben oder Chlorpropyltrichlorsilan zu neutralem Chlorpropyltriethoxysilan geben und danach Ethanol zugeben.The dosing order is irrelevant. One can Chloropropyltrichlorosilane to a solution of neutral Chloropropyltriethoxysilane and ethanol or Chloropropyltrichlorosilane to neutral Chloropropyltriethoxysilane and then add ethanol.

Chlorpropyltrichlorsilan kann in Mengen von 0,1 - 20 Gew.-%, vorzugsweise 0,5 - 5 Gew.-%, besonders bevorzugt 0,8-1,2 Gew.-%, bezogen auf Chlorpropyltriethoxysilan, zugegeben werden.Chloropropyltrichlorosilane can be used in amounts of from 0.1 to 20% by weight, preferably 0.5 to 5 wt .-%, particularly preferably 0.8 to 1.2 % By weight, based on chloropropyltriethoxysilane, be added.

Die Reaktionsmischung kann vor Zugabe von Natriumpolysulfid oder Na2S und Schwefel erwärmt werden, vorzugsweise auf Temperaturen von 20 - 90 °C.The reaction mixture may be heated before the addition of sodium polysulfide or Na 2 S and sulfur, preferably at temperatures of 20-90 ° C.

Bis(3-[triethoxysilyl]propyl)tetrasulfan, hergestellt nach dem erfindungsgemäßen Verfahren, hat eine Iodfarbzahl von ≤ 10 mg Iod/100 ml.Bis (3- [triethoxysilyl] propyl) tetrasulfane prepared according to The process according to the invention has an iodine color number of ≤ 10 mg iodine / 100 ml.

BeispieleExamples Beispiel 1:Example 1:

Bei Raumtemperatur werden zu einer Lösung aus 240,8 g Chlorpropyltriethoxysilan (neutral) in 200 ml Ethanol 2,4 g Chlorpropyltrichlorsilan getropft. Anschließend wird 1 h lang bei 82 °C unter Rühren am Rückfluß gekocht. Nach Abkühlen auf 60 °C werden 87,1 g Natriumpolysulfid zugegeben und das Reaktionsgemisch 1,5 h lang bei 82 °C unter Rühren am Rückfluß gekocht. Nach Abkühlen auf Raumtemperatur wird vom ausgefallenen Natriumchlorid abfiltriert und das Ethanol am Rotationsverdampfer entfernt. Eine nachfolgende Filtration liefert 256,1 g hellgelbes Bis(3-[triethoxysilyl]propyl)tetrasulfan mit einer Iodfarbzahl von 5-7 mg Iod/100 ml.
1H-NMR (CDCl3) :δ 0,75 (m, 6 H, Si-(CH 2)-(CH2)-(CH2)-S), 1,22 (t, 3J(HH)= 14 Hz, 18 H, Si-O-CH2-CH 3), 1,72 - 1,95 (m, 6 H, Si-(CH2)-(CH 2)-(CH2)-S), 2,65 - 3,06 (m, Si-(CH2)-(CH2)-(CH 2)-S), 3,82 (q, 3J(HH)= 14 Hz, 12 H, Si-O-CH 2-CH3).At room temperature, 2.4 g of chloropropyltrichlorosilane are added dropwise to a solution of 240.8 g of chloropropyltriethoxysilane (neutral) in 200 ml of ethanol. It is then boiled for 1 h at 82 ° C with stirring at reflux. After cooling to 60 ° C., 87.1 g of sodium polysulfide are added and the reaction mixture is refluxed for 1.5 hours at 82 ° C. with stirring. After cooling to room temperature, the precipitated sodium chloride is filtered off and the ethanol is removed on a rotary evaporator. Subsequent filtration yields 256.1 g of light yellow bis (3- [triethoxysilyl] propyl) tetrasulfane with an iodine color number of 5-7 mg iodine / 100 ml.
1 H-NMR (CDCl3): δ 0.75 (m, 6 H, Si (C H 2) - (CH 2) - (CH 2) -S), 1.22 (t, 3 J (HH ) = 14 Hz, 18 H, Si-O-CH 2 -C H 3), 1.72 - 1.95 (m, 6 H, Si (CH 2) - (C H 2) - (CH 2) -S), 2.65 - 3.06 (m, Si (CH 2 ) - (CH 2 ) - (C H 2 ) -S), 3.82 (q, 3 J (HH) = 14 Hz, 12 H, Si-OC H 2 -CH 3 ).

Beispiel 2:Example 2:

Bei Raumtemperatur werden zu 240,8 g Chlorpropyltriethoxysilan (neutral) 2,4 g Chlorpropyltrichlorsilan getropft. Anschließend wird 1 h lang bei 80 °C gerührt. Nach Zugabe von 200 ml Ethanol, die Temperatur fällt auf 62 °C ab, werden 87,1 g Natriumpolysulfid zugegeben und das Reaktionsgemisch 1,5 h lang bei 82 °C unter Rühren am Rückfluß gekocht. Nach Abkühlen auf Raumtemperatur wird vom ausgefallenen Natriumchlorid abfiltriert und das Ethanol am Rotationsverdampfer entfernt. Eine nachfolgende Filtration liefert 257,3 g hellgelbes Bis(3-[triethoxysilyl]propyl)tetrasulfan mit einer Iodfarbzahl von 7-10 mg Iod/100 ml.
1H-NMR (CDCl3) : δ 0,75 (m, 6 H, Si-(CH 2)-(CH2)-(CH2)-S), 1,22 (t, 3J(HH)= 14 Hz, 18 H, Si-O-CH2-CH 3), 1,72 - 1,95 (m, 6 H, Si-(CH2)-(CH 2)-(CH2)-S), 2,65 - 3,06 (m, Si-(CH2)-(CH2)-(CH 2)-S), 3,82 (q, 3J(HH)= 14 Hz, 12 H, Si-O-CH 2-CH3).At room temperature, 2.4 g of chloropropyltrichlorosilane are added dropwise to 240.8 g of chloropropyltriethoxysilane (neutral). The mixture is then stirred for 1 h at 80 ° C. After addition of 200 ml of ethanol, the temperature drops to 62 ° C, 87.1 g of sodium polysulfide are added and the reaction mixture is refluxed for 1.5 hours at 82 ° C with stirring. After cooling to room temperature, the precipitated sodium chloride is filtered off and the ethanol is removed on a rotary evaporator. Subsequent filtration yields 257.3 g of light yellow bis (3- [triethoxysilyl] propyl) tetrasulfane having an iodine color number of 7-10 mg iodine / 100 ml.
1 H-NMR (CDCl3): δ 0.75 (m, 6 H, Si (C H 2) - (CH 2) - (CH 2) -S), 1.22 (t, 3 J (HH ) = 14 Hz, 18 H, Si-O-CH 2 -C H 3), 1.72 - 1.95 (m, 6 H, Si (CH 2) - (C H 2) - (CH 2) -S), 2.65 - 3.06 (m, Si (CH 2 ) - (CH 2 ) - (C H 2 ) -S), 3.82 (q, 3 J (HH) = 14 Hz, 12 H, Si-OC H 2 -CH 3 ).

Beispiel 3:Example 3:

Bei Raumtemperatur werden zu einer Lösung aus 1122 kg Chlorpropyltriethoxysilan (neutral) in 950 kg Ethanol 11,4 kg Chlorpropyltrichlorsilan gegeben. Anschließend wird 30 min. lang bei Raumtemperatur gerührt. Danach werden 390 kg Natriumpolysulfid zugegeben und das Reaktionsgemisch 1 h lang bei 82 °C unter Rühren am Rückfluß gekocht. Nach Abkühlen auf Raumtemperatur wird vom ausgefallenen Natriumchlorid abfiltriert und das Ethanol im Vakuum entfernt. Eine nachfolgende Filtration liefert 1250 kg hellgelbes Bis(3-[triethoxysilyl]propyl)tetrasulfan mit einer Iodfarbzahl von 5-7 mg Iod/100 ml.
1H-NMR (CDCl3) : δ 0,75 (m, 6 H, Si-(CH 2)-(CH2)-(CH2)-S), 1,22 (t, 3J(HH)= 14 Hz, 18 H, Si-O-CH2-CH 3), 1,72 - 1,95 (m, 6 H, Si-(CH2)-(CH 2)-(CH2)-S), 2,65 - 3,06 (m, Si-(CH2)-(CH2)-(CH 2)-S), 3,82 (q, 3J(HH)= 14 Hz, 12 H, Si-O-CH 2-CH3).At room temperature, 11.4 kg of chloropropyltrichlorosilane are added to a solution of 1122 kg of chloropropyltriethoxysilane (neutral) in 950 kg of ethanol. Subsequently, 30 min. stirred long at room temperature. Thereafter, 390 kg of sodium polysulfide are added and the reaction mixture for 1 h at 82 ° C with stirring under reflux. After cooling to room temperature, the precipitated sodium chloride is filtered off and the ethanol is removed in vacuo. Subsequent filtration yields 1250 kg of light yellow bis (3- [triethoxysilyl] propyl) tetrasulfane with an iodine color number of 5-7 mg iodine / 100 ml.
1 H-NMR (CDCl3): δ 0.75 (m, 6 H, Si (C H 2) - (CH 2) - (CH 2) -S), 1.22 (t, 3 J (HH ) = 14 Hz, 18 H, Si-O-CH 2 -C H 3), 1.72 - 1.95 (m, 6 H, Si (CH 2) - (C H 2) - (CH 2) -S), 2.65 - 3.06 (m, Si (CH 2 ) - (CH 2 ) - (C H 2 ) -S), 3.82 (q, 3 J (HH) = 14 Hz, 12 H, Si-OC H 2 -CH 3 ).

Beispiel 4Example 4

Bei Raumtemperatur werden zu einer Lösung aus 481,6 g Chlorpropyltriethoxysilan (neutral) in 450 ml Ethanol 4,8 g Chlorporpyltrichlorsilan getropft. Anschließend wird 1 h lang bei 80 °C unter Rühren am Rückfluß gekocht. Nach Abkühlen auf 58 °C werden 89,8 g Natriumsulfid und 105,8 g Schwefel zugegeben und das Reaktionsgemisch 1,5 h lang bei 82 °C unter Rühren am Rückfluß gekocht. Nach Abkühlen auf Raumtemperatur wird vom ausgefallenen Natriumchlorid abfiltriert und das Ethanol am Rotationsverdampfer entfernt. Eine nachfolgende Filtration liefert 500,4 g hellgelbes Bis(3-[triethoxysilyl]propyl)tetrasulfan mit einer Iodfarbzahl von 5-7 mg Iod/100 ml).
1H-NMR (CDCl3) : δ 0,75 (m, 6 H, Si-(CH 2)-(CH2)-(CH2)-S), 1,22 (t, 3J(HH)= 14 Hz, 18 H, Si-O-CH2-CH 3), 1,72 - 1,95 (m, 6 H, Si-(CH2)-(CH 2)-(CH2)-S), 2,65 - 3,06 (m, Si-(CH2)-(CH2)-(CH 2)-S), 3,82 (q, 3J(HH)= 14 Hz, 12 H, Si-O-CH 2-CH3).At room temperature, 4.8 g Chlorporpyltrichlorsilan are added dropwise to a solution of 481.6 g of chloropropyltriethoxysilane (neutral) in 450 ml of ethanol. It is then boiled for 1 h at 80 ° C with stirring at reflux. After cooling to 58 ° C., 89.8 g of sodium sulfide and 105.8 g of sulfur are added and the reaction mixture is refluxed for 1.5 hours at 82 ° C. with stirring. After cooling to room temperature, the precipitated sodium chloride is filtered off and the ethanol is removed on a rotary evaporator. Subsequent filtration provides 500.4 g of light yellow bis (3- [triethoxysilyl] propyl) tetrasulfane with an iodine color number of 5-7 mg iodine / 100 ml).
1 H-NMR (CDCl3): δ 0.75 (m, 6 H, Si (C H 2) - (CH 2) - (CH 2) -S), 1.22 (t, 3 J (HH ) = 14 Hz, 18 H, Si-O-CH 2 -C H 3), 1.72 - 1.95 (m, 6 H, Si (CH 2) - (C H 2) - (CH 2) -S), 2.65 - 3.06 (m, Si (CH 2 ) - (CH 2 ) - (C H 2 ) -S), 3.82 (q, 3 J (HH) = 14 Hz, 12 H, Si-OC H 2 -CH 3 ).

Beispiel 5 (Vergleichsbeispiel 1):Example 5 (Comparative Example 1):

Bei 60 °C werden zu einer Lösung aus 240,8 g Chlorpropyltriethoxysilan (neutral) in 200 ml Ethanol 87,1 g Natriumpolysulfid zugegeben und das Reaktionsgemisch 1,5 h lang bei 82 °C unter Rühren am Rückfluß gekocht. Nach Abkühlen auf Raumtemperatur wird vom ausgefallenen Natriumchlorid abfiltriert und das Ethanol am Rotationsverdampfer entfernt. Eine nachfolgende Filtration liefert 255,0 g rotes Bis(3-[triethoxysilyl]propyl)tetrasulfan mit einer Iodfarbzahl von > 20 mg Iod/100 ml.
1H-NMR (CDCl3) : δ 0,75 (m, 6 H, Si-(CH 2)-(CH2)-(CH2)-S), 1,22 (t, 3J(HH)= 14 Hz, 18 H, Si-O-CH2-CH 3), 1,72 - 1,95 (m, 6 H, Si-(CH2)-(CH 2)-(CH2)-S), 2,65 - 3,06 (m, Si-(CH2)-(CH2)-(CH 2)-S), 3,82 (q, 3J(HH)= 14 Hz, 12 H, Si-O-CH 2-CH3).At 60 ° C., 87.1 g of sodium polysulfide are added to a solution of 240.8 g of chloropropyltriethoxysilane (neutral) in 200 ml of ethanol, and the reaction mixture is refluxed for 1.5 hours at 82 ° C. with stirring. After cooling to room temperature, the precipitated sodium chloride is filtered off and the ethanol is removed on a rotary evaporator. Subsequent filtration yields 255.0 g of red bis (3- [triethoxysilyl] propyl) tetrasulfane with an iodine color number of> 20 mg iodine / 100 ml.
1 H-NMR (CDCl3): δ 0.75 (m, 6 H, Si (C H 2) - (CH 2) - (CH 2) -S), 1.22 (t, 3 J (HH ) = 14 Hz, 18 H, Si-O-CH 2 -C H 3), 1.72 - 1.95 (m, 6 H, Si (CH 2) - (C H 2) - (CH 2) -S), 2.65 - 3.06 (m, Si (CH 2 ) - (CH 2 ) - (C H 2 ) -S), 3.82 (q, 3 J (HH) = 14 Hz, 12 H, Si-OC H 2 -CH 3 ).

Beispiel 6 (Vergleichsbeispiel 2):Example 6 (Comparative Example 2):

Bei Raumtemperatur werden 240,8 g Chlorpropyltriethoxysilan (neutral) in 200 ml Ethanol vorgelegt. Anschließend werden 30 ml einer 1-molaren Ethanolischen HCl-Lösung zugegeben und 30 min. lang bei RT gerührt. Nach Zugabe von 87,1 g Natriumpolysulfid wird das Reaktionsgemisch 1,5 h lang bei 82 °C unter Rühren am Rückfluß gekocht. Nach Abkühlen auf Raumtemperatur wird vom ausgefallenen Natriumchlorid abfiltriert und das Ethanol am Rotationsverdampfer entfernt. Eine nachfolgende Filtration liefert 253,5 g rotes Bis(3-[triethoxysilyl]propyl)tetrasulfan mit einer Iodfarbzahl von > 20 mg Iod/100 ml.At room temperature, 240.8 g of chloropropyltriethoxysilane (neutral) in 200 ml of ethanol. Then be Added 30 ml of a 1 molar ethanolic HCl solution and 30 min. stirred at RT for a long time. After addition of 87.1 g Sodium polysulfide, the reaction mixture for 1.5 h at 82 ° C with stirring at reflux. After cooling to Room temperature is the precipitated sodium chloride filtered off and the ethanol on a rotary evaporator away. Subsequent filtration yields 253.5 g red bis (3- [triethoxysilyl] propyl) tetrasulfane with a Iodine color number of> 20 mg iodine / 100 ml.

Beispiel 7 (Vergleichsbeispiel 3):Example 7 (Comparative Example 3):

Bei 60 °C werden zu einer Lösung aus 481,6 g Chlorpropyltriethoxysilan (neutral) in 450 ml Ethanol 89,8 g Natriumsulfid und 105,8 g Schwefel zugegeben und das Reaktionsgemisch 1,5 h bei 82 °C unter Rühren am Rückfluß gekocht. Nach Abkühlen auf Raumtemperatur wird vom ausgefallenen Natriumchlorid abfiltriert und das Ethanol am Rotationsverdamper entfernt. Eine nachfolgende Filtration liefert 496,3 g rotes Bis (3-[triethoxysilyl]propyl)tetrasulfan mit einer Iodfarbzahl von > 20 mg Iod/100 ml.
1H-NMR (CDCl3) : δ 0,75 (m, 6 H, Si-(CH 2)-(CH2)-(CH2)-S), 1,22 (t, 3J(HH)= 14 Hz, 18 H, Si-O-CH2-CH 3), 1,72 - 1,95 (m, 6 H, Si-(CH2)-(CH 2)-(CH2)-S), 2,65 - 3,06 (m, Si-(CH2)-(CH2)-(CH 2)-S), 3,82 (q, 3J(HH)= 14 Hz, 12 H, Si-O-CH 2-CH3).At 60 ° C 89.8 g of sodium sulfide and 105.8 g of sulfur are added to a solution of 481.6 g of chloropropyltriethoxysilane (neutral) in 450 ml of ethanol and the reaction mixture was heated at 82 ° C for 1.5 h with stirring at reflux. After cooling to room temperature, the precipitated sodium chloride is filtered off and the ethanol is removed on a rotary evaporator. Subsequent filtration yields 496.3 g of red bis (3- [triethoxysilyl] propyl) tetrasulfane with an iodine color number of> 20 mg iodine / 100 ml.
1 H-NMR (CDCl3): δ 0.75 (m, 6 H, Si (C H 2) - (CH 2) - (CH 2) -S), 1.22 (t, 3 J (HH ) = 14 Hz, 18 H, Si-O-CH 2 -C H 3), 1.72 - 1.95 (m, 6 H, Si (CH 2) - (C H 2) - (CH 2) -S), 2.65 - 3.06 (m, Si (CH 2 ) - (CH 2 ) - (C H 2 ) -S), 3.82 (q, 3 J (HH) = 14 Hz, 12 H, Si-OC H 2 -CH 3 ).

Beispiel 8:Example 8:

Bei Raumtemperatur werden zu 20 ml Chlorpropyltriethoxysilan (neutral) 5 ml Chlorpropyltrichlorsilan getropft. Anschließend wird 1 h lang bei 80 °C gerührt. Nach Abkühlen auf Raumtemperatur werden vom erhaltenen Reaktionsgemisch und zur Kontrolle vom eingesetzten Chlorpropyltriethoxysilan (neutral) GC-MS Spektren aufgenommen (Figur 1 und 2). Die Zugabe von Chlorpropyltrichlorsilan zu neutralem Chlorpropyltriethoxysilan führt zur Bildung von Chlorpropylmonochlordiethoxysilan und Chlorpropyldichlormonoethoxysilan.At room temperature, add to 20 ml Chloropropyltriethoxysilane (neutral) 5 ml Chloropropyltrichlorosilane added dropwise. Then 1 h stirred long at 80 ° C. After cooling to room temperature are from the resulting reaction mixture and to control Chloropropyltriethoxysilane (neutral) GC-MS used Spectra recorded (Figure 1 and 2). The addition of Chloropropyltrichlorosilane to neutral Chloropropyltriethoxysilane leads to the formation of Chloropropylmonochlorodiethoxysilane and Chloropropyldichloromonoethoxysilane.

GC: HP 5890 II; MS: Finnigan MAT 95; Säule: 30 m x 0,25 mm DB-5MS; df: 0,25 µm U026; Helium: 80 kPa; Temp.: 50(5)-5-100-15-300(10); Split: 100 ml/min; Inj.vol.: 0,1 µl gelöst in n-Hexan.GC: HP 5890 II; MS: Finnigan MAT 95; Column: 30 m x 0.25 mm DB-5MS; df: 0.25 μm U026; Helium: 80 kPa; Temp .: 50 (5) -5-100-15-300 (10); Split: 100 ml / min; Inj.vol .: 0.1 μl dissolved in n-hexane.

Die Iodfarbzahl wird nach DIN 6162 bestimmt.The iodine color number is determined according to DIN 6162.

Claims (3)

  1. Process for the preparation of yellow bis(3-[triethoxysilyl]propyl)tetrasulfane having an iodine colour value of ≤ 10 mg of iodine/100 ml, characterised in that chloropropyltrichlorosilane is added to neutral chloropropyltriethoxysilane and reaction with sodium polysulfide or with Na2S and sulfur in ethanol is then carried out.
  2. Process according to claim 1, characterised in that chloropropyltrichlorosilane is added in an amount of from 0.1 to 20 wt.%.
  3. Process according to claim 1, characterised in that the reaction mixture is heated to from 20 to 90°C before the addition of sodium polysulfide or of Na2S and sulfur.
EP01111617A 2000-05-13 2001-05-12 Process for preparing yellow bis(3-[triethoxysilyl]propyl)tetrasulfan Expired - Lifetime EP1153927B1 (en)

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DE10045269A1 (en) * 2000-09-13 2002-03-28 Degussa Process for the preparation of yellow bis (3- [triethoxysilyl] propyl) polysulfane
DE10132939C1 (en) * 2001-07-06 2003-01-30 Degussa Process for the preparation of yellow bis (3- [trialkoxysilyl] alkyl) polysulfanes
DE10351736B3 (en) * 2003-11-06 2005-01-13 Degussa Ag Preparation of (mercaptoorganyl)alkoxysilanes comprises reacting alkali metal sulfide with mixture of (haloorganyl)alkoxysilane and (haloorganyl)halosilane in alcohol with exclusion of air and at elevated pressure
DE10351735B3 (en) * 2003-11-06 2004-12-09 Degussa Ag Production of mercaptoorganyl alkoxysilanes comprises reacting an alkali metal hydrogen sulfide with a mixture of haloorganyl alkoxysilane and haloorganyl halosilane
DE102007037556A1 (en) 2007-08-09 2009-02-12 Evonik Degussa Gmbh Process for the preparation of alkylpolyether-substituted mercaptosilanes

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DE2061189C3 (en) * 1970-12-11 1974-12-05 Wacker-Chemie Gmbh, 8000 Muenchen Process for the continuous production of alkoxysilanes or alkoxypolysiloxanes
DE2141159C3 (en) * 1971-08-17 1983-11-24 Degussa Ag, 6000 Frankfurt Organosilicon compounds containing sulfur
DE3236628C2 (en) * 1982-10-04 1986-09-11 Dynamit Nobel Ag, 5210 Troisdorf Process for the continuous production of alkoxysilanes
DE19819373A1 (en) * 1998-04-30 1999-11-04 Degussa Process for the preparation of mixtures of organosilicon oligosulfanes with a high proportion of organanosilicon disulfanes
DE19829390A1 (en) * 1998-07-01 2000-01-05 Degussa New oligomeric organosilicon compounds, their use in rubber mixtures and for the production of moldings
US6172251B1 (en) * 1998-07-24 2001-01-09 The Goodyear Tire & Rubber Company Solid/liquid phase transfer system
US6294683B1 (en) * 1999-01-19 2001-09-25 The Goodyear Tire & Rubber Company Solid/liquid phase transfer system
DE19930495C1 (en) * 1999-07-01 2000-11-09 Degussa Alkoxysilylalkylpolysulfide compounds, useful assistants in the production of silica filled rubber, made by reacting silyl alkyl halides with alkali polysulfides obtained by reacting alkali hydroxides with sulfur in non-aqueous solvent

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